Formaldehyde → Diethyl P-[[[(4-methylphenyl)sulfonyl]oxy]methyl]phosphonate

HRID 439585Notes

Reaction equation

HRID 439585 reaction equation
[P:1]([O-:8])([O:5][CH2:6][CH3:7])[O:2][CH2:3][CH3:4].[CH2:9]=[O:10].C(N(CC)CC)C.[C:18]1([CH3:28])[CH:23]=[CH:22][C:21]([S:24](Cl)(=[O:26])=[O:25])=[CH:20][CH:19]=1>C1(C)C=CC=CC=1>[C:18]1([CH3:28])[CH:23]=[CH:22][C:21]([S:24]([O:10][CH2:9][P:1](=[O:8])([O:5][CH2:6][CH3:7])[O:2][CH2:3][CH3:4])(=[O:26])=[O:25])=[CH:20][CH:19]=1

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 73974-Toluenesulfonyl chlorideHCID 8471Triethylamine2×HCID 3780918Diethylphosphite

Product 1

HCID 4193599Diethyl P-[[[(4-methylphenyl)sulfonyl]oxy]methyl]phosphonate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of diethyl phosphite (700 g, 5.07 mmole), paraformaldehyde (190 g, 6.33 mole) and triethylamine (51.0 g, 0.50 mole) in toluene (2.8 L) is heated ca 2 hr at 85°-90° C., then under relux for ca 1 h. The resulting solution is cooled to ca. 0° C., and checked by NMR (CDCl3) for completion of the reaction (in-process control). Then p-toluenesulfonyl chloride (869 g, 4.56 mole) and triethylamine (718 g, 7.09 mole) are added with cooling (0°-10° C.). The resulting mixture is stirred at ca. 22° C. for 17-24 h and checked by NMR (CDCl3) for completion of the reaction (in-process control). The solids are removed by vacuum filtration. The filtrate is washed with water (2×) and dried over anhydrous magnesium sulfate. The solvent is evaporated in vacuo to give the title compound as an oil in 65-75% (1060-1225 g) yield. As an in-process control, NMR (CDCl3) is obtained and the product purity is assayed by HPLC C18 -35% CH3CN in KH2PO4 (0.02M)!. The purity of the product is typically 85-95%.

Workup

  1. temperatureis heated ca 2 hr at 85°-90° C.
  2. waitunder relux for ca 1 h
  3. customchecked by NMR (CDCl3) for completion of the reaction (in-process control)
  4. temperaturewith cooling (0°-10° C.)
  5. customchecked by NMR (CDCl3) for completion of the reaction (in-process control)
  6. customThe solids are removed by vacuum filtration
  7. washThe filtrate is washed with water (2×)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customThe solvent is evaporated in vacuo

Sources & evidence

ORD record
ord-b80b980474044801991166c72a45aed7
Source dataset
uspto-grants-1996_05
Patent number
US05514798

Reaction notes

Loading…